Alkoxylation using modified group iiib metal-containing bimetallic or polymetallic catalysts

ABSTRACT

This invention relates to modified Group IIIB metal-containing bimetallic or polymetallic catalysts and the use thereof in the preparation of alkoxylation products, i.e., condensation reaction products of alkylene oxides and organic compounds having at least one active hydrogen. In another aspect of this invention, processes are provided for preparing the modified Group IIIB metal-containing bimetallic or polymetallic catalysts for alkoxylation using a Group IIIB metal or a Group IIIB metal-containing compound as sources for the catalytically-active Group IIIB metal. In a further aspect of this invention, processes are provided for preparing alkoxylation products that have beneficial, narrow molecular weight ranges using the modified Group IIIB metal-containing bimetallic or polymetallic catalysts.

RELATED APPLICATIONS

The following are related, commonly assigned applications, filed on aneven date herewith:

U.S. Patent application Ser. No. 251,430, now U.S. Pat. No. 4,946,984U.S. patent application Ser. No. 251,434; U.S. patent application Ser.No. 251,433; U.S. patent application Ser. No. 251,432 and U.S. patentapplication Ser. No. 251,431.

BRIEF SUMMARY OF THE INVENTION Technical Field

This invention relates to modified Group IIIB metal-containingbimetallic or polymetallic catalysts and the use thereof in thepreparation of alkoxylation products, i.e., condensation reactionproducts of alkylene oxides and organic compounds having at least oneactive hydrogen. In another aspect of the invention, processes areprovided for preparing the modified Group IIIB metal-containingbimetallic or polymetallic catalysts for alkoxylation using a Group IIIBmetal or a Group IIIB metal-containing compound, e.g., lanthanum oxide,as sources for the catalytically-active Group IIIB metal. In a furtheraspect of the invention, processes are provided for preparingalkoxylation products that have beneficial, narrow molecular weightranges using the modified Group IIIB metal-containing bimetallic orpolymetallic catalysts.

Background of the Invention

A variety of products such as surfactants, functional fluids, glycolethers, polyols, and the like, are commercially prepared by thecondensation reaction of alkylene oxides with organic compounds havingat least one active hydrogen, generally, in the presence of an alkalineor acidic catalyst. The types and properties of the alkoxylationproducts depend on, among other things, the active hydrogen compound,the alkylene oxide, and the mole ratio of alkylene oxide to organiccompound employed, as well as the catalyst. As a result of thealkoxylation, a mixture of condensation product species are obtainedhaving a range of molecular weights.

In many applications of alkoxylated products, certain of thealkoxylation species provide much greater activity than others.Consequently, alkoxylation processes are desired that are selective tothe production of those alkoxylation species. Further, for many of theseuses, mixtures of alkoxylation products falling within a narrow range ofmolecular distribution of reacted alkylene oxide are believed to besuperior to alkoxylation products in which a single alkoxylation speciepredominates. For example, in a surfactant composition the range ofmaterials on which the surfactant will be required to operate willnormally vary. A range of alkoxylation species, even though narrow, willenhance the performance of the surfactant to the variety of materialswhich it may encounter. Further, mixtures closely related alkoxylationspecies can provide a mixture having other improved properties such asin respect to cloud point, freezing point, pour point and viscosity ascompared to a single specie. There, however, is a balance, and if thedistribution of species becomes too broad, not only are less desirablealkoxylation species diluting the mixture, but also the more hydrophilicor lipophilic components than those in the sought range can bedetrimental to the sought properties.

Moreover, a wide range of alkoxylation species can restrict theflexibility in ultimate product formulation using the alkoxylationreaction product. For example, in making oil-in-water emulsion productsit is often desired to prepare a concentrated composition that minimizesthe weight percent of water. This concentrate may then be diluted withwater at the time of use, thereby saving the expense of shipping andstoring water. The ability to form a desirable concentrate is generallydependent, in part, on having a narrow distribution of alkoxylationspecies since if heavier moieties are present, a greater portion ofwater is usually required otherwise gelling (evidencing productinstability) may occur.

The recognition that certain distributions of moles of alkylene oxide tomoles of organic compound in alkoxylation products can be important haslong been recognized. For example, British Patent Specification No.1,399,966 discloses the use of ethoxylates having ahydrophilic-lipophilic balance (HLB) of from about 10 to about 13.5 foruse in a laundry detergent. In order to provide this HLB, the moles ofethylene oxide reacted per mole of fatty alcohol is described as beingcritical. In British Patent Specification No. 1,462,133, the soughtcleaning composition employed alkylene oxide cosurfactants sufficient toprovide even a narrower HLB, i.e., from about 10 to about 12.5. InBritish Specification No. 1,462,134, a detergent composition isdisclosed which uses ethoxylates having an HLB of from about 9.5 to11.5, with the preferred ethoxylates having an HLB of 10.0 to 11.1.

Thus, with the increased understanding of the properties to be providedby an alkoxylation product, greater demands are placed on tailoring themanufacture of the alkoxylation product to enhance the soughtproperties. Accordingly, efforts have been expended to providealkoxylated products in which the distribution of reacted alkylene oxideunits per mole of organic compound is limited to a range in which thesought properties are enhanced.

Alkoxylation processes are characterized by the condensation reaction inthe presence of a catalyst of at least one alkylene oxide with at leastone organic compound containing at least one active hydrogen. Perhapsthe most common catalyst is potassium hydroxide. The products made usingpotassium hydroxide, however, generally exhibit a broad distribution ofalkoxylate species. See, for example, M. J. Schick, NonionicSurfactants, Volume 1, Marcel Dekker, Inc., New York, N.Y. (1967) pp. 28to 41. That is, little selectivity to particular alkoxylate species isexhibited, especially at higher alkoxylation ratios. For example, FIG. 6of U.S. Pat. No. 4,223,164 depicts the distribution of alkoxylatespecies prepared by ethoxylating a fatty alcohol mixture with 60 weightpercent ethylene oxide using a potassium catalyst.

The distribution that will be obtained in alkoxylation processes canvary even using the same type of catalyst depending upon the type oforganic compound being alkoxylated. For example, with nonylphenol, aPoisson-type distribution can be obtained using a potassium hydroxidecatalyst. However, with aliphatic alcohols such as decanol, dodecanol,and the like, the distribution is even broader. These distributions arereferred to herein as "Conventional Broad Distributions".

Acidic catalysts can also be used, and they tend to produce a narrower,and thus more desirable, molecular weight distributions; however, theyalso contribute to the formation of undesired by-products and, thus, arenot in wide use commercially.

Particular emphasis has been placed on controlling molecular weightdistribution of alkoxylation products. One approach has been to stripundesirable alkoxylate species from the product mixture. For instance,U.S. Pat. No. 3,682,849 discloses processes for the vapor phase removalof unreacted alcohol and lower boiling ethoxylate components. Thecompositions are said to contain less than about 1% of each ofnon-ethoxylated alcohols and monoethoxylates, less than 2% by weight ofdiethoxylates and less than 3% by weight of triethoxylates. This processresults in a loss of raw materials since the lower ethoxylates areremoved from the composition. Also, the stripped product still has awide distribution of ethoxylate species, i.e., the higher molecularweight products are still present in the composition to a significantextent. To circumvent viscosity problems which would normally exist withstraight-chain alcohols, about 20 to 30 percent of the starting alcoholis to be branched according to the patent.

Obtaining a narrower distribution of alkoxylated species at lowerepoxide reactant to organic compound mole ratios can be readilyaccomplished. U.S. Pat. No. 4,098,818 discloses a process in which themole ratio of catalyst (e.g., alkali metal and alkali metal hydride) tofatty alcohol is about 1:1. Ethoxylate distributions are disclosed forParts C and D of Example 1 and are summarized as follows:

    ______________________________________                                                        Part C  Part D                                                ______________________________________                                        Primary fatty alcohol                                                                           12 carbons                                                                              12 to 14                                                                      carbons                                           Moles of ethylene oxide                                                                         3.5       3                                                 per mole of alcohol                                                           Product molecular 352       311                                               weight                                                                        Average ethoxylation                                                                            3.8       2.54                                              Distribution, %                                                               E.sub.0           0.7       3.8                                               E.sub.1           6.3       15.3                                              E.sub.2           17.3      25.9                                              E.sub.3           22.4      23.8                                              E.sub.4           21.2      15.9                                              E.sub.5           15.6      10.7                                              E.sub.6           8.6       3.5                                               E.sub.7           5.6       1.2                                               E.sub.8           2.3       --                                                ______________________________________                                    

The high catalyst content in combination with the low alkylene oxide toalcohol ratio appears to enable a narrow, low ethoxylate fraction to beproduced. However, as the ratio of alkylene oxide to alcohol increases,the characteristic, Conventional Broad Distribution of alkali metalcatalysts can be expected. Moreover, even though the disclosed processis reported to provide a narrower distribution of ethoxylate species,the distribution is skewed so that significant amounts of the higherethoxylates are present. For example, in Part C, over 15 percent of theethoxylate compositions had at least three more oxyethylene groups thanthe average based on the reactants, and that amount in Part D is over 16percent.

European Patent Application No. A0095562, Published Dec. 12, 1983,exemplifies the ability to obtain high selectivity to low ethoxylatespecies when low ratios of ethylene oxide reactant to alcohol areemployed as well as the tendency to rapidly lose that selectivity whenhigher ethoxylated products are sought. For instance, Example 1,(described as a 1 mole EO adduct), which reports the use of adiethylaluminum fluoride catalyst, employs 300 grams of a 12 to 14carbon alcohol and 64 grams of ethylene oxide and Example 5, (describedas a 1.5 mole EO adduct) using the same catalyst, employs a weight ratioof alcohol to ethylene oxide at 300:118. Based on the graphicallypresented data, the distributions appear to be as follows:

    ______________________________________                                                   Example 1                                                                             Example 5                                                  ______________________________________                                        E.sub.0      27        10                                                     E.sub.1      50        36                                                     E.sub.2      17        33                                                     E.sub.3       4        16                                                     E.sub.4      --         6                                                     E.sub.5      --         2                                                     E.sub.6      --         1                                                     ______________________________________                                    

Even with a small increase in ethoxylation from the described 1 mole EOadduct to the described 1.5 mole adduct, the distribution of ethoxylatespecies broadened considerably with more of the higher ethoxylates beingproduced as can be expected from a Conventional Broad Distribution. Itmay be that the catalyst is consumed in the reaction process so that itis not available to provide the narrower distributions of alkoxylationproduct mixtures at the high adduct levels.

Several catalysts have been identified that are reported to providemolecular weight distributions for higher ethoxylates that are narrowerthan those expected from a Conventional Broad Distribution. Inparticular, this work has emphasized ethoxylation catalysis byderivatives of the Group IIA alkaline earth metals. Interest in thesecatalysts, which to date has been confined almost exclusively to theproduction of non-ionic surfactants, stems from their demonstratedcapability for providing hydrophobe ethoxylates having narrowermolecular weight distributions, lower unreacted alcohol contents, andlower pour points than counterparts manufactured with conventionalalkali metal-derived catalysts.

Recently, Yang and coworkers were granted a series of U.S. patents whichdescribe primarily the use of unmodified or phenolic-modified oxides andhydroxides of barium and strontium as ethoxylation catalysts forproducing non-ionic surfactants exhibiting lower pour Points, narrowermolecular weight distributions, lower unreacted alcohol contents andbetter detergency than counterpart products prepared by state-of-the-artcatalysis with alkali metal hydroxides. See U.S. Pat. Nos. 4,210,764;4,223,164; 4,239,917; 4,254,287; 4,302,613 and 4,306,093.

The molecular weight distributions of the ethoxylates disclosed in thesepatents, while being narrower than conventional distributions, appearnot to meet fully the desired narrowness. For example, FIG. 6 of U.S.Pat. No. 4,223,146 depicts the product distribution of an ethoxylate ofa 12 to 14 carbon alcohol and 60 percent ethylene oxide using variouscatalysts. A barium hydroxide catalyst is described as providing aproduct mixture containing, as the most prevalent component, about 16percent of the six mole ethoxylate. The distribution is, however, stillrelatively wide in that the ethoxylate species having three or moreoxyethylene groups than the most prevalent component is above about 19weight percent of the mixture and the distribution is skewed towardhigher ethoxylates. The strontium hydroxide catalyst run which is alsodepicted on that figure appears to have a more symmetrical distributionbut the most prevalent component, the seven mole ethoxylate, is presentin an amount of about 14.5 weight percent and about 21 weight percent ofthe composition had three or more oxyethylene groups than the mostprevalent component.

Also, U.S. Pat. No. 4,239,917 discloses ethoxylate distributions usingbarium hydroxide catalyst and a fatty alcohol. FIG. 7 of that patentillustrates the distribution at the 40 percent ethoxylation level withthe four mole ethoxylate being the most prevalent component. Over about19 weight percent of the mixture has three or more oxyethylene groupsthan the most prevalent component. FIG. 4 depicts the distribution ofethoxylation at the 65 percent ethoxylation level. The nine and ten moleethoxylates are the most prevalent and each represent about 13 weightpercent of the composition. The distribution is relatively symmetricalbut about 17 weight percent of the composition has at least three moreoxyethylene groups than the average peak (9.5 oxyethylene groups).Interestingly, comparative examples using sodium hydroxide catalyst aredepicted on each of these figures and evidence the peaking that can beachieved with conventional base catalysts at low ethoxylation levels,but not at higher ethoxylation levels.

McCain and co-workers have published a series of European patentapplications describing the catalytic use of basic salts of alkalineearth metals especially calcium, which are soluble in the reactionmedium. These applications further disclose catalyst preparationprocedures involving alcohol exchange in respect to the alkoxy moiety ofthe metal alkoxide catalytic species. See European patent publicationNo. 0026544, No. 0026547, and No. 0026546, all herein incorporated byreference. These workers have also disclosed the use of strong acids topartially neutralize and thereby promote the catalytic action of certainalkaline earth metal derivatives. See U.S. Pat. No. 4,453,022 and U.S.Pat. No. 4,453,023 (barium-containing catalyst), both hereinincorporated by reference.

The calcium-containing catalysts disclosed by McCain et al. provideenhanced selectivities to higher alkoxylate species as compared tomixtures produced using conventional potassium hydroxide catalyst.Indeed, bases exist to believe that these calcium-containing catalystsprovide narrower distributions of alkoxylates than those provided bystrontium- or barium-containing catalysts. However, there is still needfor improvement in providing a narrower yet distribution of alkoxylationproducts, particularly a distribution in which at least one componentconstitutes at least 20 weight percent of the composition andalkoxylation products having more than three alkoxyl groups than theaverage peak alkoxylation component comprise very little of the productmixture.

U.S. Pat. Nos. 4,754,075, 4,886,917 and 4,820,673, herein incorporatedby reference, relates to processes for preparing alkoxylation mixtureshaving relatively narrow alkoxylation product distributions usingmodified, calcium-containing catalysts. Processes are also disclosed formaking alkoxylation catalysts using calcium oxide and/or calciumhydroxide as sources for the catalytically-active calcium. Thealkoxylation product mixtures disclosed therein have a narrow andbalanced distribution of alkoxylation species. The disclosed productmixtures are relatively free from large amounts of substantially higheralkoxylation moieties, i.e., those having at least three more alkoxylgroups than the average peak alkoxylate specie. It is stated thereinthat narrow distributions can be obtained where the most prevalentalkoxylation moiety has four or greater alkoxy units, that is, in theregions in which conventional catalysts provide a relatively wide rangeof alkoxylation, species.

U.S. Pat. No. 4,902,658 herein incorporated by reference, relates toheterogeneous (organic polymer-supported) calcium-containing catalystsand the use thereof in the preparation of alkoxylation products, i.e.,condensation reaction products of alkylene oxides and organic compoundshaving at least one active hydrogen. Processes are provided forpreparing heterogeneous (organic polymer-supported) calcium-containingcatalysts for alkoxylation using calcium oxide or calcium hydroxide assources for the catalytically-active calcium. Alkoxylation products areprovided that have beneficial, narrow molecular weight ranges and areessentially neutral in pH and free from catalyst residues.

DISCLOSURE OF THE INVENTION

This invention relates to modified Group IIIB metal-containingbimetallic and polymetallic alkoxylation catalysts and to processes formaking the catalysts using a Group IIIB metal or a Group IIIBmetal-containing compound, e.g., lanthanum oxide, as sources for thecatalytically-active Group IIIB metal. This invention further relates toprocesses for preparing alkoxylation product mixtures having relativelynarrow alkoxylation product distributions using the modified Group IIIBmetal-containing bimetallic and polymetallic catalysts. As used herein,Group IIIB metals shall include scandium, yttrium, lanthanum, cerium,praseodymium, neodymium, promethium, samarium, europium, gadolinium,terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium,thorium, protactinium, uranium and plutonium. Also, as used herein,Group IIA metals shall include beryllium, magnesium, calcium, strontium,barium and radium.

The modified Group IIIB metal-containing bimetallic and polymetalliccatalysts of this invention are modified with an organic or inorganicoxyacid having a divalent or polyvalent anion such as sulfuric acid,phosphoric acid, carbonic acid, pyrosulfuric acid and the like, or by adivalent or polyvalent metal salt of an organic or inorganic oxyacidsuch as aluminum sulfate, zinc sulfate, zinc phosphate and the like.Mixtures of divalent or polyvalent oxyacids, e.g., sulfuric acid andphosphoric acid, mixtures of divalent or polyvalent metal salts ofoxyacids, e.g., aluminum sulfate and zinc phosphate, and mixtures ofdivalent or polyvalent oxyacids and divalent or polyvalent metal saltsof oxyacids, e.g., sulfuric acid and zinc phosphate, can be used in theprocesses of this invention. The divalent or polyvalent oxyacids and thedivalent or polyvalent metal salts of oxyacids are at times referred tohereinafter as "modifiers". These modified catalysts are believed tohave complex structures which are probably comprised of a mixture ofspecies, certain of which may not even be catalytically active. Thosespecies which are catalytically active are believed to have structuresof the type depicted by the following formula:

    [R.sub.1 --X.sub.1 --M.sub.1 ].sub.f --Y.sub.1 --[M.sub.3 --Y.sub.2 ].sub.j --[M.sub.2 --X.sub.2 --R.sub.2 ].sub.g                    (i)

wherein:

R₁ and R₂ are independently hydrogen or an organic residue of an organiccompound having at least one active hydrogen;

X₁ and X₂ are independently oxygen, sulfur or nitrogen;

M₁, M₂ and M₃ are independently a divalent or polyvalent metal otherthan a Group IIA metal provided at least one of M₁, M₂ and M₃ is a GroupIIIB metal;

Y₁ and Y₂ are independently a divalent or polyvalent oxyacid anion ofvalence 2 to 6, oxygen, sulfur or nitrogen provided at least one of Y₁and Y₂ is a divalent or polyvalent oxyacid anion of valence 2 to 6;

j is an integer having a value of from 0 to about 100; and

f and g are integers having a value such that the sum f+g is equal tothe valence of Y₁ when j is a value of 0, and f and g are integershaving a value such that the sum f+g is equal to the valence of Y₁ plus[M₃ --Y₂ ]_(j) when j is a value other than 0. It is understood thatformula (i) is speculation only. As used herein, divalent shall mean avalence of 2 and polyvalent shall mean a valence of more than 2. Also,as used herein, bimetallic shall mean 2 metals which can be the same ordifferent and polymetallic shall mean more than 2 metals which can bethe same or different.

For purposes of this invention including the claims hereinafter, it isunderstood that formula (i) shall be inclusive of polyvalencyrequirements for M₁, M₂ and M₃ and that such polyvalency requirementsare appropriately satisfied in formula (i). It is also understood thatany polyvalency requirements of M₃ may be satisfied by R₁ --X₁ -- or R₂--X₂ --.

Another aspect of the invention provides a method for preparing amodified Group IIIB metal-containing bimetallic or polymetallicalkoxylation catalyst, which method comprises (i) reacting orsolubilizing, at least in part, a Group IIIB metal or a Group IIIBmetal-containing compound, e.g., lanthanum oxide, by mixing with anactivator to form a Group IIIB metal-containing composition havingtitratable alkalinity, (ii) reacting a divalent or polyvalent metalother than a Group IIA metal or a divalent or polyvalentmetal-containing compound other than a Group IIA metal-containingcompound with an organic compound having at least one active hydrogen toproduce a divalent or polyvalent metal-containing composition, (iii)reacting the Group IIIB metal- containing composition with the divalentor polyvalent metal-containing composition under effective reactionconditions to produce a catalyst precursor composition, and (iv)reacting the catalyst precursor composition with an oxyacid having adivalent or polyvalent anion or a divalent or polyvalent metal salt ofan oxyacid or mixtures thereof under effective reaction conditions toproduce the alkoxylation catalyst. Steps (i) and (ii) may be carried outconcurrently using the same reaction equipment. The term "solubilizing"as used herein is intended to mean that the Group IIIB metal is providedin an active form; however, the term is not intended to be limiting tothe formation of a truly dissolved Group IIIB metal specie (which may ormay not exist).

The solubilization is effected by mixing certain Group IIIBmetal-containing compounds, for example, with an activator having thegeneral formula Z_(a) --X--Q--Y--Z'_(b) wherein X and Y are the same ordifferent electronegative (relative to carbon), hetero (i.e.,non-carbon) atoms selected from the group consisting of oxygen,nitrogen, sulfur and phosphorous; a and b are the same or differentintegers satisfying the valency requirements of X and Y; Q is anyorganic radical which is electropositive or essentially neutral relativeto X and/or Y, which does not prevent the solubilization, and whichcontains at least one carbon atom and preferably has the formula:##STR1## wherein R₄ and R₅ are the same or different and are selectedfrom the group consisting of hydrogen and lower alkyl or alkylene groupsof one to four carbon atoms, and p is an integer from 1 to 6, preferably2 to 4; Z and Z. are the same or different and are either hydrogen or anorganic radical which does not interfere with the function of theactivator for its intended purpose, i.e., its solubilizing and/orstabilizing function, thereby forming the Group IIIB metal-containingcomposition which is then reacted with the divalent or polyvalentmetal-containing composition to produce the catalyst precursorcomposition. The catalyst precursor composition is then reacted with thedivalent or polyvalent oxyacid or the divalent or polyvalent metal saltof the oxyacid to produce a catalyst which is catalytically active inthe alkoxylation of compounds having active hydrogens, especiallyalcohols.

Solubilization of a Group IIIB metal-containing compound can result inthe production of an alkaline slurry, which alkalinity can be detectedand measured by titration and which is referred to herein as "titratablealkalinity".

The modified Group IIIB metal-containing bimetallic or polymetalliccatalyst composition can be directly contacted with alkylene oxides toform alkoxylates of the activator itself, if having an active hydrogen,to produce alkoxylates. If the activator does not have an activehydrogen, excess activator should preferably be removed prior toalkoxylation.

According to further embodiments of this aspect of the invention, anexchange reaction is carried out either prior to or after the reactionof the catalyst precursor composition with the oxyacid having a divalentor polyvalent anion or the divalent or polyvalent metal salt of anoxyacid under conditions at which an exchange reaction will occur, withat least one organic compound having an active hydrogen, e.g., analcohol, having a higher boiling point (and usually a longer carbonchain length) than said activator to form the corresponding,catalytically active higher boiling derivative of the catalyst precursorcomposition. This latter catalytic species can then be directlycontacted with alkylene oxide to form alkoxylates of the higher boilingmaterial.

The alkoxylation processes of this invention involve the condensationreaction of an alkylene oxide and at least one organic compound havingat least one active hydrogen in the presence of a catalyticallyeffective amount of a modified Group IIIB metal-containing bimetallic orpolymetallic catalyst as described above. The modifier is employed in anamount of about 0.2 to 0.9, e.g., 0.35 to 0.85, often, about 0.45 to0.75, times that required to give a normal equivalence of metal toanion, which is sufficient to narrow the distribution of thealkoxylation product mixture and provide at least one alkoxylationspecie in an amount of at least about 20 weight percent of the mixture.The modified Group IIIB metal-containing bimetallic or polymetalliccatalyst is prepared under sufficient agitation to ensure a relativelyuniform product. The preferred oxyacid anion is the phosphoric acidanion. Frequently, the modified Group IIIB metal-containing catalyst isprepared in a medium having a dielectric constant at 25° C. or itsnormal boiling point, whichever is less, of at least about 10,preferably, at least about 20, say, about 20 to 50, and frequently about25 or 30 to 45.

By this invention, alkoxylation product mixtures are provided which havea narrow, but balanced distribution of alkoxylation species. Theseproduct mixtures are relatively free from large amounts of substantiallyhigher alkoxylation moieties, i.e, those having at least three morealkoxyl groups than the average peak alkoxylate specie. Advantageously,these narrow distributions can be obtained where the most prevalentalkoxylation moiety has four or greater alkoxy units, that is, in theregions in which conventional catalysts provide a relatively wide rangeof alkoxylation species.

The alkoxylation product mixtures prepared by the processes of thisinvention are characterized as the condensation reaction products ofalkylene oxides and organic compounds having at least one activehydrogen in which the mole ratio of reacted alkylene oxide per activehydrogen is at least about 4, say, about 4 to 16 or 24, preferably about5 to 12. The product mixtures have at least one alkoxylation moietywhich constitutes at least about 20, say, about 20 to 30 or 40, and mostoften about 20 to 30, weight percent of the composition. Thealkoxylation mixtures of this invention also have a relativelysymmetrical distribution. Hence, the portion of the product mixturehaving three or more oxyalkylene unit groups (per active hydrogen siteof the organic compound) than the peak alkoxylation specie is relativelyminor, e.g., often less than about 12, say, less than 10, and oftenabout 1 to 10, weight percent of the mixture. Similarly, thealkoxylation species having fewer oxyalkylene groups (per activehydrogen site of the organic compound) by three or more oxyalkylenegroups from the average peak alkoxylation specie is usually relativelyminor, e.g., less than about 15, say, less than about 10, often about0.5 to 10, weight percent of the composition. Generally, the oneoxyalkylene unit higher and the one oxyalkylene unit lower alkoxylatesin respect to the most prevalent alkoxylation specie are present in aweight ratio to the most prevalent alkoxylation specie of about 0.6:1 to1:1.

The preferred alkoxylation product mixtures of this invention correspondto the formula

    P.sub.n =A×e.sup.-(n-n).spsp.2.sup./(2.6+0.4n)

wherein n is the number of oxyalkylene groups per reactive hydrogen sitefor an alkoxylation specie (n must equal at least one) of thecomposition, n is the weight average oxyalkylene number, A is the weightpercent of the most prevalent alkoxylation specie in the mixture andP_(n) is, within plus or minus two percentage points, the weight percentof the alkoxylation specie having n oxyalkylene groups (per activehydrogen site) in the mixture. This distribution relationship generallyapplies where n is between the amount of n minus 4 to the amount of nplus 4.

For purposes herein, the average peak alkoxylation specie is defined asthe number of oxyalkylene groups (per active hydrogen site) of the mostprevalent alkoxylation specie when the next higher and lower homologsare each present in a weight ratio to the most prevalent alkoxylationspecie of less than 0.9:1. When one of the adjacent homologs is presentin a weight ratio greater than that amount, the average peakalkoxylation specie has an amount of oxyalkylene groups equal to thenumber average of those of the two species. The weight averageoxyalkylene number is the weight average of the oxyalkylene groups ofthe alkoxylation species in the mixture (including unreacted alcohol),i.e., n equals the sum of (n)(P_(n)) for all the species present dividedby 100.

Preferred alkoxylation product mixtures of this invention includepoly(oxyethylene)glycols, i.e., CARBOWAX® and fatty alcohol ethoxylates,i.e., TERGITOL®. CARBOWAX® is the registered trademark of Union CarbideCorporation for a series of poly(oxyethylene)glycols. Ethylene glycolcan be used to make the CARBOWAX® poly(oxyethylene)glycols or theCARBOWAX® poly(oxyethylene)glycols can be used to make higher molecularweight CARBOWAX® poly(oxyethylene)glycols. For example, CARBOWAX®poly(oxyethylene)glycol 200 can be used to make CARBOWAX®poly(oxyethylene)glycol 400. Specifically, the CARBOWAX®poly(oxyethylene)glycols are liquid and solid polymers of the generalformula H(OCH₂ CH₂)_(w) OH, where w is greater than or equal to 4. Ingeneral, each CARBOWAX® poly(oxyethylene)glycol is followed by a numberwhich corresponds to its average molecular weight. Generally, theinvention process is not preferred for using CARBOWAX®poly(oxyethylene)glycols having an average molecular weight above about600 to 800 as starting materials because such CARBOWAX®poly(oxyethylene)glycols are solids at room temperature (although theyare liquid at the reaction temperatures, e.g., 110° C.). Examples ofuseful CARBOWAX® poly(oxyethylene)glycols are: CARBOWAX®poly(oxyethylene)glycol 200, which has an average w value of 4 and amolecular weight range of 190 to 210; CARBOWAX® poly(oxyethylene)glycol400, which has an average w value between 8.2 and 9.1 and a molecularweight range of 380 to 420; and CARBOWAX® poly(oxyethylene)glycol 600,which has an average w value between 12.5 and 13.9 and a molecularweight range of 570 to 630.

TERGITOL® is the registered trademark of Union Carbide Corporation for aseries of ethoxylated nonylphenols, primary and secondary alcohols,i.e., nonionic surfactants, and the sodium salts of the acid sulfate ofsecondary alcohols of 10 to 20 carbon atoms, i.e., anionic surfactants.Examples of the TERGITOL® nonionic surfactants include TERGITOL® SNonionics which have the general formula CH₃ (CH₂)_(x) CH(CH₃)--O--(CH₂CH₂ O)_(y) H wherein x is a value of 9-11 and y is a value of aboutgreater than 1. Examples of the TERGITOL® anionic surfactants includeTERGITOL® Anionic 08, which is C₄ H₉ CH(C₂ H₅)CH₂ SO₄ --Na; TERGITOL®Anionic 4, which is C₄ H₉ CH(C₂ H₅)C₂ H₄ CH--(SO₄ Na)CH₂ CH(CH₃)₂ ; andTERGITOL® Anionic 7, which is C₄ H₉ CH(C₂ H₅)C₂ H₄ CH--(SO₄ Na)C₂ H₄CH(C₂ H₅)₂.

DETAILED DESCRIPTION

As indicated above, the modified Group IIIB metal-containing bimetallicor polymetallic catalysts of this invention are modified with an organicor inorganic oxyacid having a divalent or polyvalent anion such assulfuric acid, phosphoric acid, carbonic acid, pyrosulfuric acid and thelike, or by metal salts of organic or inorganic oxyacids having divalentor polyvalent anions such as aluminum sulfate, zinc sulfate, zincphosphate and the like or mixtures thereof. These modified catalysts arebelieved to have complex structures which are probably comprised of amixture of species, certain of which may not even be catalyticallyactive. Those species which are catalytically active are believed tohave structures of the type depicted by the following formula:

    [R.sub.1 --X.sub.1 --M.sub.1 ].sub.f --Y.sub.1 --[M.sub.3 --Y.sub.2 ].sub.j --[M.sub.2 --X.sub.2 --R.sub.2 ].sub.g                    (i)

wherein:

R₁ and R₂ are independently hydrogen or an organic residue of an organiccompound having at least one active hydrogen;

X₁ and X₂ are independently oxygen, sulfur or nitrogen;

M₁, M₂ and M₃ are independently a divalent or polyvalent metal otherthan a Group IIA metal provided at least one of M₁, M₂ and M₃ is a GroupIIIB metal;

Y₁ and Y₂ are independently a divalent or polyvalent oxyacid anion ofvalence 2 to 6, oxygen, sulfur or nitrogen provided at least one of Y₁and Y₂ is a divalent or polyvalent oxyacid anion of valence 2 to 6;

j is an integer having a value of from 0 to about 100; and

f and g are integers having a value such that the sum f+g is equal tothe valence of Y₁ when j is a value of 0, and f and g are integershaving a value such that the sum f+g is equal to the valence of Y₁ plus[M₃ --Y₂ ]_(j) when j is a value other than 0. It is understood thatformula (i) is speculation only.

The alkoxylation product mixtures of this invention are enabled by theuse of modified Group IIIB metal-containing bimetallic or polymetalliccatalysts that have been modified by strong, divalent or polyvalentoxyacids or divalent or polyvalent metal salts of strong oxyacids ormixtures thereof sufficient to provide a defined narrow distribution ofalkoxylation products. The alkoxylation conditions may otherwise varywhile still obtaining a narrower distribution of alkoxylate products.

The modifier of the catalyst is a divalent or polyvalent acid or adivalent or polyvalent metal salt of an oxyacid or mixtures thereof andcontains at least one, most often at least about 2, oxygen atoms thatare conventionally depicted as double bonded to the nucleus atom. Suchacids and metal salts include, for example, sulfuric and phosphoric acidand the sulfates and phosphates of zirconium, zinc and thorium; however,in general the most narrow distributions are obtained using phosphoricacid and the metal phosphates.

The types of divalent and polyvalent anions of oxyacids and metal saltsof oxyacids suitable for use in this invention, e.g., Y₁ and Y₂, includeby way of example only, sulfates, e.g., SO₄ ⁻², phosphates, e.g., PO₄⁻³, manganates, e.g., MnO₄ ⁻², titanates, e.g., TiO₃ ⁻², tantalates,e.g., Ta₂ O₆ ⁻², molybdates, e.g., MoO₄ ⁻², vanadates, e.g., V₂ O₄ ⁻²,chromates, e.g., CrO₄ ⁻², zirconates, e.g., ZrO₃ ⁻², polyphosphates andthe like.

Illustrative of metals which may be included in the divalent orpolyvalent metal salt modifier and also in the divalent or polyvalentmetal-containing compositions described hereinafter include scandium,yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium,tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt,nickel, copper, zinc, cadmium, mercury, boron, aluminum, gallium,indium, thallium, carbon, silicon, germanium, tin, lead, phosphorus,arsenic, antimony, sulfur, selenium, tellurium, cerium, praseodymium,neodymium, promethium, samarium, europium, gadolinium, terbium,dysprosium, holmium, erbium, thulium, ytterbium, lutetium, thorium,protactinium, uranium and plutonium.

The amount of modifier employed and the manner in which it is introducedto prepare the catalyst can be determinative of whether the desirednarrow distribution with at least one alkoxylation specie being presentin an amount of at least about 20 weight percent of the composition, isachieved. While not wishing to be limited to theory, it is believed thatactive catalysts for producing narrow distributions of alkoxylationproducts comprises a Group IIIB metal atom and another metal atom(s)other than a Group IIA metal atom(s) in association with the modifieranion in a manner in which the Group IIIB metal atom and/or metalatom(s) is activated as illustrated by formula (i) hereinabove. Theamount of modifier added is in an amount of about 0.2 to 0.9, say, about0.45 to 0.75, times that required to give a normal equivalence of metalto anion.

In general, at the time of modification, the catalyst precursorcomposition may be represented by the following formula:

    [R.sub.1 --X.sub.1 --M.sub.1 ].sub.f --X.sub.3 --[M.sub.3 --X.sub.4 ].sub.j [M.sub.2 --X.sub.2 --R.sub.2 ].sub.g                      (ii)

wherein R₁, R₂, X₁, X₂, M₁, M₂, M₃, j, f and g are as definedhereinabove and X₃ and X₄ are independently oxygen, sulfur or nitrogen.R₁ and R₂ independently may also contain double bonded oxygen (theorganic compound was a carboxylic acid), heteroatom such as oxygen,sulfur, nitrogen and phosphorous (e.g., the organic compound was aglycol, polyamine, ether of a glycol or the like). Frequently, R₁ and R₂may comprise 1 to 20 carbons. It is understood that formula (ii) isspeculation only.

For purpose of this invention including the claims hereinafter, it isunderstood that formula (ii) shall be inclusive of polyvalencyrequirements for M₁, M₂ and M₃ and that such polyvalency requirementsare appropriately satisfied in formula (ii). It is also understood thatany polyvalency requirements of M₃ may be satisfied by R₁ --X₁ -- or R₂--X₂ --.

The modifier appears to enable the desired catalytically active modifiedGroup IIIB metal-containing species to form; however, it has been foundthat depending upon other conditions during the modification, differentamounts of modifier will provide the optimum catalyst in terms ofselectivity and reaction rate during an alkoxylation process.Accordingly, an aspect of the invention is providing a level ofmodification sufficient to achieve the narrow distribution of alkoxylateproduct mixtures.

The medium containing the modified Group IIIB metal-containingbimetallic or polymetallic catalyst can also affect whether theresulting modified Group IIIB metal-containing bimetallic orpolymetallic catalyst enables the desired narrow distribution ofalkoxylation products to be formed. If the medium comprises as thepredominant component, i.e., solvent, a material that has a lowdielectric constant, the modifier can form a separate liquid phase andincreased difficulty in obtaining an intimate admixture may be observed.On the other hand, with solvents that are too polar, the organic moietyin association with the Group IIIB metal atom or other metal atom may bedisplaced with the solvent. Accordingly, undue amounts of water aretypically avoided during the modification of the Group IIIBmetal-containing catalyst. Most often, the medium and the organiccompound providing the moiety on the Group IIIB metal atom or othermetal atom(s) are the same. Particularly convenient media includeethylene glycol, propylene glycol, diethylene glycol, glycerol,butanediols, 1,3-propanediol, and the like. Conveniently, the mediumemployed, if not intended to be a reactant for producing alkoxylates,should have a sufficiently low boiling point that can readily be removedfrom the catalyst and organic compound reactant mixture by distillation.Most often, the medium comprises a solvent having at least twoheteroatoms such as the activators described herein.

The modifier is preferably added while the catalyst precursorcomposition is being vigorously agitated. In this regard, a slowaddition of the modifier to the catalyst precursor composition ispreferred. Generally, less than 10 percent of the modifier to be addedis added to the catalyst precursor composition at any one time. Theaddition of the modifier can be conducted at a convenient temperature,e.g., about 10° C. to 160° C., say, about 50° C. to 150° C. Preferably,a nitrogen atmosphere is advantageous. It may be advantageous tointroduce the modifier in aqueous form.

The Group IIIB metal-containing bimetallic or polymetallic catalysthaving substituents of the formulae R₁ X₁ -- and --X₂ R₂ may be preparedin any suitable manner. For example, a Group IIIB metal-containingcomposition can be prepared by reacting a Group IIIB metal or a GroupIIIB metal-containing compound such as lanthanum oxide or other suitablesources of Group IIIB metals described below with an organic compoundcontaining an active hydrogen atom of the formula R₁ X₁ H or HX₂ R₂. Adivalent or polyvalent metal-containing composition other than a GroupIIA metal-containing composition can be prepared by reacting a divalentor polyvalent metal described hereinabove or other suitable source ofdivalent or polyvalent metal with an organic compound containing anactive hydrogen atom of the formula R₁ X₁ H or HX₂ R₂. The Group IIIBmetal-containing composition and the divalent or polyvalentmetal-containing composition are then reacted under effective reactionconditions to produce a catalyst precursor composition. With compoundshaving higher molecular weights, e.g., 4 or more carbons, it isgenerally preferred to use a lower molecular weight and more reactiveand volatile compound of the formulae R₁ X₁ H or HX₂ R₂ (e.g., of 1 toabout 3 carbons, especially compounds such as ethanol, ethylamine,ethylene glycol and the like) and then exchange that substituent withthe higher molecular weight substituent while removing the lowermolecular weight material by volatilization. The catalyst precursorcomposition is then reacted with a divalent or polyvalent oxyacid or adivalent or polyvalent metal salt of an oxyacid to produce the modifiedGroup IIIB metal-containing bimetallic and polymetallic alkoxylationcatalyst.

The compounds having the formulae R₁ X₁ H and HX₂ R₂ include thoseorganic compounds having active hydrogens described in connection withthe alkoxylation products of this invention, such as alcohols, phenols,carboxylic acids and amines. Most often, the compounds having theformulae R₁ X₁ H and HX₂ R₂ are alcohols. When an exchange reaction isto be conducted to provide a higher molecular weight substituent on theGroup IIIB metal atom or other metal atom(s), it is generally preferredto conduct the modification prior to exchange and use a lower molecularweight material for the replacement substituent to enhance themodification process. Suitable organic compounds having active hydrogensfor use in this invention include the products ofhydroformylation/hydrogenation reactions.

Illustrative of Group IIIB metal-containing compounds/compositions foruse in this invention include soluble Group IIIB metal-containingcompounds/compositions per se or Group IIIB metal-containingcompounds/compositions which can be converted to a soluble form uponinteraction with the alkoxylation process reactants, e.g., activator.Examples of specific Group IIIB metal-containing compounds/compositionsinclude one or more reaction products of Group IIIB metal with variousalcohols (alcoholates such as Group IIIB metal alkoxides and phenoxides)as well as oxide, hydroxide, ammoniate, amide, thiolate, carbide,thiophenoxide, nitride, thiocyanate and carboxylate compounds, e.g.,acetates, formates, oxalates, citrates, benzoates, laurates andstearates. The preferred Group IIIB metal-containing compounds arelanthanum-containing compounds or mixtures thereof, and the preferredGroup IIIB metal-containing compositions are lanthanum alcoholates.

The preparation of the modified Group IIIB metal-containing bimetallicor polymetallic catalyst composition from a Group IIIB metal or a GroupIIIB metal-containing compound such as lanthanum oxide or other suitablesource of Group IIIB metal described above and a divalent or polyvalentmetal other than a Group IIA metal or suitable source of the divalent orpolyvalent metal is typically conducted at elevated temperatures, e.g.,from about 30° C. to 200° C. or more, and in a liquid medium. Theorganic compound which provides the substitution is normally provided inexcess of that required for reaction with the Group IIIBmetal-containing reactant and/or divalent or polyvalent metal-containingreactant. Hence, the weight ratio of Group IIIB metal-containingreactant and divalent or polyvalent metal-containing reactant to theorganic compound frequently is within the range of about 0.01:100 to25:100. The reaction may, if desired, be conducted in the presence of aninert liquid solvent. The exchange reaction is also conducted underelevated temperature and, optionally, under reduced pressure tofacilitate removal of the more volatile components. Temperatures mayrange from about 50° C. to 250° C., say, about 80° C. to 200° C. or 250°C., and pressures (absolute) are often in the range of 1 millibar to 5bars, e.g., about 10 millibars to 2 bars.

It is usually desired that the organic substituent on the modified GroupIIIB metal-containing bimetallic or polymetallic catalyst compositioncorrespond to the "starter" component for the alkoxylation process. Thestarter component is the organic compound having at least one activehydrogen with which the alkylene oxide reacts.

The alkoxylation is conducted using a catalytically-effective amount ofthe Group IIIB metal-containing bimetallic or polymetallic catalyst,e.g., about 0.001 to 10, often about 0.5 to 5, weight percent based onthe weight of the starter component. The catalysts substantially retaintheir activities during the alkoxylation, regardless of the amount ofalkylene oxide employed. Thus, the amount of catalyst can be based onthe amount of starter provided to the alkoxylation zone and not thedegree of alkoxylation to be effected.

Normally, the Group IIIB metal-containing bimetallic or polymetalliccatalyst and the starter component are admixed and then the alkyleneoxide is added at the reaction temperature until the desired amount ofalkylene oxide has been added, then the product is neutralized and canbe finished, if desired, in any procedure including stripping unreactedstarter material from the product mixture, filtration, or furtherreaction.

The temperature of the alkoxylation is sufficient to provide a suitablerate of reaction and without degradation of the reactants or reactionproducts. Often, the temperatures range from between about 50° C. and270° C., e.g. from about 100° C. to 200° C. The pressure may also varywidely, but when low-boiling alkylene oxides such as ethylene oxide andpropylene oxide are employed, a pressurized reactor is preferably used.

The alkoxylation reaction medium is preferably agitated to ensure a gooddispersal of the reactants and catalyst throughout the reaction medium.Also, the alkylene oxide is usually added at a rate approximating thatwhich it can be reacted.

Neutralization may assist in the recovery of the catalyst from thealkoxylation product mixture. When neutralizing, acids that may tend toform catalyst-containing gel structures or solids that clog filteringapparatus should be avoided. Conveniently, sulfuric acid, phosphoricacid, propionic acid, benzoic acid and the like are used.

The present invention provides a preferred procedure whereby a GroupIIIB metal or a Group IIIB metal-containing compound can be effectivelyused to prepare catalytic species which are active in the alkoxylationor organic compounds having at least one active hydrogen such asalcohols, especially long-chain fatty alcohols, carboxylic acids,amines, polyols and phenols. This is accomplished by the followinggeneral procedure.

A Group IIIB metal-containing composition is prepared by contacting aGroup IIIB metal or a Group IIIB metal-containing compound with anactivator under conditions at which the Group IIIB metal or Group IIIBmetal-containing compound and the activator will react or interact toform one or more catalytically active derivatives, which are thenreacted with a divalent or polyvalent metal-containing composition otherthan a Group IIA metal-containing composition under conditions effectiveto form one or more catalytically active derivatives, hereinafterreferred to collectively as "the catalyst precursor composition". Theactivator may be any compound having the formula

    Z.sub.a --X--Q--Y--Z'.sub.b

wherein the various terms are as previously defined. Group IIIBmetal-containing bimetallic or polymetallic alkoxylation catalystsincorporating the catalyst precursor compositions of this reaction areespecially effective in the alkoxylation of alcohols, particularlyprimary alcohols such as the long-chain fatty alcohols, or mixturesthereof, which are used as starters in the manufacture of nonionicsurfactants. However, Group IIIB metal-containing bimetallic orpolymetallic alkoxylation catalysts incorporating the catalyst precursorcomposition can also be effectively used in the catalytic reaction of awide variety of organic compounds containing active hydrogen. If, forexample, the activator is ethylene glycol, the catalyst precursorcomposition can readily be utilized in situ to catalyze the alkoxylationof ethylene glycol itself, thereby producing ethylene glycol-startedpoly(oxyalkylene)glycols of any desired nominal molecular weight andadvantageously having a relatively narrow molecular weight distribution.

If, by way of further example, the activator is the monoethyl ether ofethylene glycol (MEEG) and the catalyst precursor composition isdirectly alkoxylated with ethylene oxide, the product will be a mixtureof ethoxylates of MEEG whose composition will be determined by the molarratio of ethylene oxide to MEEG.

As used herein, the term "excess activator" means that amount ofactivator which is not chemically or physically bound to a Group IIIBmetal or metal(s) other than Group IIA metals and thus can be removed bysimple physical means. The technique employed for this operation is notcritical. Vacuum stripping is recommended for its simplicity andefficiency, but evaporation and other known procedures may also be used.

The catalyst precursor composition will be obtained as a finely divided,particulate solid, in slurry form, which can be readily separated fromthe reaction mixture by filtration, decantation, or similar procedures.The product so obtained is catalytically active in alkoxylationreactions, whether or not modified with a divalent or polyvalent oxyacidor a divalent or polyvalent metal salt of an oxyacid.

It is a particularly desirable feature of this invention that thecatalyst can be used to provide alkoxylate surfactants having a uniquelynarrow molecular weight distribution, low pour point, and low level ofunreacted starter component. In this usage, the catalyst is contactedwith the starter component, e.g., alcohol, under conditions at whichreaction will occur, to perform an alcohol-exchange (which can also bereferred to as an alkoxide exchange) reaction. A portion of the starteralcohol thus is present as an alcoholate of a Group IIIB metal, whichalcoholate is itself an active species for the alkoxylation reaction.This reaction mixture is then reacted with one or more alkylene oxides,e.g., alkylene oxides such as ethylene oxide, according to knownprocedures to produce the desired surfactant.

Referring now to the structural formula given above for the activator, Xand Y are preferably more than one carbon removed from each other, e.g.,in the beta position relative to each other, and are preferably oxygen,as in ethylene glycol, or oxygen and nitrogen, as in monoethanolamine;however, X and Y can also be sulfur or phosphorous. Exemplary of otheruseful compounds are ethylenediamine, N-methylethanolamine,tetrahydrofurfuryl alcohol, 2-mercaptoethanol, 1,2-propylene glycol,2-methylthioethanol, 2-ethoxyethanol, diethylene glycol, 1,3-propanedioland 1,4-butanediol.

Z and Z' are the same or different radicals, optionally substituted, andoften at least one of Z and Z' is selected from the group consisting ofhydrogen, lower linear or branched alkyl of one to four carbon atoms,alkylene from two or about six carbon atoms, phenyl or loweralkyl-substituted phenyl, cycloalkyl of three to about six carbon atomsand alkylene or heteroatom-substituted alkylene rings.

In the activator, Q may comprise a carbon chain of up to six carbonsbetween X and Y. A two- to four-carbon chain is preferred, however,because the activating capacity of X and Y is maximized at such chainlengths. Of these, a two-carbon chain length is especially preferred. Inhighly preferred embodiments, Q will be a two-carbon chain and thestructural formula will be as follows: ##STR2## wherein Z, Z', X, Y, aand b are as defined hereinabove and R₆, R₇, R₈, and R₉ are preferablyhydrogen, but may also be lower alkyl or alkylene groups of one to fourcarbon atoms, optionally substituted, or such other radicals as do notinterfere with the usefulness of the activator for its intended purpose.

Also, Q may be cyclic, preferably cycloalkyl of six or fewer carbons,optionally substituted, as can be represented by the formula: ##STR3##Compounds coming within this description would include4-methoxycyclohexane 1,2-diol; 2-aminocyclopentanol; and2-methoxycyclopentanol.

Similarly, either X or Y or both of them could be part of a ringstructure with a carbon atom adjacent to either of them, as illustratedby the formula: ##STR4## Some compounds illustrating such configurationswould include tetrahydrofurfuryl alcohol; furfuryl alcohol;2-hydroxyethyl aziridine; 1-(N-methyl-2-pyrrolidinyl) ethanol; and2-aminomethylpyrrolidine.

Moreover, X and Y can themselves be part of the same ring structure,including Q, according to the formula: ##STR5## Exemplary of suchcompounds would be piperazine; 4-hydroxymethyl-2,2-dimethyl-1,3dioxolane; 2,6-dimethylmorpholine; and cyclohexanone ethylene ketal.

Numerous other ring structures, whether saturated or unsaturated,substituted or unsubstituted, are also possible and are intended to bewithin the scope of the present invention.

The only perceived limitation on Q and on the overall structure of theformula is that the activator must be capable of solubilizing, at leastin part, the Group IIIB metal-containing compound. The solubilization isconsidered to be an important step which permits certain inoperablematerials to be successfully utilized. Without intending to be bound toany particular theory, this solubilization is believed to beaccomplished through the electron-withdrawing effects of heteroatoms Xand Y in relation to adjacent carbon atoms, thereby increasing theacidity of the activator molecule and also helping it to participate inthe formation of complexes with the Group IIIB metal, such asexemplified by the structure: ##STR6## It is understood that the valencyrequirements of M₁ in the above structure are appropriately satisfied by(ZO) and O(Z).

Thus, any structure represented by the formula

    Z.sub.a --X--Q--Y--Z'.sub.b

is satisfactory, provided only that it does not eliminate or neutralizethe electronegativity of the heteroatoms and thus prevent the activatorfrom performing its intended purpose of solubilizing, at least in part,the Group IIIB metal-containing compound. In the method for preparingthe modified Group IIIB-metal-containing bimetallic or polymetalliccatalysts of this invention, it is believed that the activator mayprovide a stabilizing effect, e.g., thermal stability at hightemperatures, for certain intermediate catalytic species prepared insaid method, thereby permitting formation of the desired finalcatalytically active species.

As the Group IIIB metal-containing compound is solubilized, thealkalinity of the medium increases; thus, the building of alkalinity canbe used as a screening technique to identify potentially usefulactivators. In this test, one should look for approximately one or moregrams of alkalinity, calculated as Group IIIB metal-containing compound,based on 5 grams of Group IIIB metal-containing compound (calculated asGroup IIIB metal-containing compound) charged, as determined bytitration with 0.01N HCl in ethanol (alcoholic HCl), as will bedescribed more fully below. It should be noted, however, that aminesinterfere with this test, thus, it cannot be dependably used withamine-containing activator candidates.

In the solubilizing step of the process of this invention, as has beenmentioned above, a Group IIIB metal-containing compound or mixturesthereof are mixed with the activator to form one or more precursorspecies. The purpose of this treatment is to solubilize sufficient GroupIIIB metal-containing compound to be catalytically effective in analkoxylation reaction; thus, the Group IIIB metal-containing compoundconcentration could be either below or above its solubility maximum inthe activator, provided only that sufficient Group IIIB metal-containingcompound is solubilized to be catalytically effective. As a generalguideline, however, the concentration of Group IIIB metal-containingcompound used in the initial step should typically be in the range ofabout 1-2%, based on the activator. The Group IIIB metal-containingcompound should normally be present somewhat in excess of its solubilityin the activator, but Group IIIB metal-containing compoundconcentrations exceeding about 30% would rarely be considered desirable.

The temperature for this procedure is not considered critical, and canrange from about 50° C. up to the boiling point of the activator,typically well over 200° C. It is desirable to operate in the range ofabout 90° to 150° C., preferably about 125° to 150° C., and the systemcan be put under either vacuum or pressure to maintain any desiredtemperature while maintaining the activator in the liquid phase.Advantageously, the conditions of temperature and pressure are such thatwater can be vaporized and removed from the reaction medium. Preferablythe catalyst preparation is conducted under a substantially inertatmosphere such as a nitrogen atmosphere.

To perform this step of the process, a Group IIIB metal-containingcompound is simply added to the activator in a stirred vessel undersufficient agitation to create a slurry of the Group IIIBmetal-containing compound for a period of time adequate to solubilize atleast a portion of the Group IIIB metal-containing compound. Normally,this will be accomplished within a period of about 1 to 4 hours. Theamount of Group IIIB metal-containing compound which will be solubilizedwill depend, of course, on the concentration of Group IIIBmetal-containing compound present, the effectiveness of the activatorused, and on the temperature, time and agitation employed. Ideally, thequantity of Group IIIB metal-containing compound desired for thesubsequent alkoxylation reaction is solubilized. The source of the GroupIIIB metal-containing compound for this step includes any commercially-available grade of Group IIIB metal-containing compound, since minorimpurities contained in such Group IIIB metal-containing compounds arenot believed to significantly adversely affect the catalyst formed bythe procedures of this invention.

To prepare a divalent or polyvalent metal-containing composition, anappropriate divalent or polyvalent metal-containing compound, e.g., ametal acetate, described hereinbelow can be reacted with an organiccompound having at least one active hydrogen. The resulting mixture willbe heated at reflux at a temperature of from about 80° C. to about 200°C. by adjusting pressure on the reaction system. Normally, such heatingwill be accomplished within a period of about 2 to 6 hours whileconcurrently removing byproducts of reaction, e.g., water, overhead.

It is understood that bimetallic and polymetallic salts can be used inthe processes of this invention. For example, the Group IIIBmetal-containing compound and the divalent or polyvalentmetal-containing compound other than a Group IIA-metal containingcompound can be the same compound for purposes of this invention.Illustrative of such bimetallic or polymetallic salts include, forexample, lanthanum titanate (La₂ O₃ 2TiO₂), cerium tungstate (Ce₂(WO₄)₃) and the like.

The Group IIIB metal-containing composition is then reacted with thedivalent or polyvalent metal-containing composition under effectiveconditions to produce a catalyst precursor composition which is reactedwith a divalent or polyvalent acid or a divalent or polyvalent metalsalt of an oxyacid to produce a catalyst for alkoxylation reactions andenhance the narrowness of the alkoxylation product. This would be thecase where, for example, ethylene oxide is to be added to the materialused as the activator, e.g., ethylene glycol, to producepoly(oxyethylene)glycols of any desired molecular weight.

The divalent or polyvalent metal-containing compositions used in thisinvention can be represented by the formulae [R₁ X₁ ]_(m) [M₁ ]_(n) and[R₂ X₂ ]_(m), [M₂ ]_(n), wherein R₁, R₂, X₁, X₂, M₁ and M₂ are asdefined hereinabove and m, n, m' and n' are the same or differentintegers satisfying the appropriate valency requirements. The divalentor polyvalent metal-containing compositions can be prepared bycontacting a divalent or polyvalent metal other than a Group IIA metaldescribed hereinabove or other suitable source of divalent or polyvalentmetal with an organic compound containing an active hydrogen atom of theformulae R₁ X₁ H or HX₂ R₂. Such divalent or polyvalent metal-containingcompositions can be prepared by conventional methods.

Illustrative of divalent or polyvalent metal-containingcompounds/compositions for use in this invention include solubledivalent or polyvalent metal-containing compounds/compositions per se ordivalent or polyvalent metal-containing compounds/compositions which canbe converted to a soluble form upon interaction with the alkoxylationprocess reactants, e.g., activator. Examples of specific divalent orpolyvalent metal-containing compounds/compositions include one or morereaction products of the divalent or polyvalent metal other than a GroupIIA metal with various alcohols (alcoholates such as aluminum alkoxidesand phenoxides) as well as oxide, hydroxide, ammoniate, amide, thiolate,carbide, thiophenoxide, nitride, thiocyanate and carboxylate compounds,e.g., acetates, formates, oxalates, citrates, benzoates, laurates andstearates.

The reaction of the Group IIIB metal-containing composition with thedivalent or polyvalent metal-containing composition is conducted undereffective conditions to produce a catalyst precursor composition. Thisreaction can be conducted by conventional methods such as described inU.S. Pat. No. 3,432,445, U.S. Pat. No. 3,607,785 and U.S. Pat. No.4,281,087. Alternatively, the catalyst precursor composition can beprepared from a Meerwein double alkoxide by controlledhydrolysis/solvolysis. See Bradley, D. C., Mehrotra, R. C. and Gaur, D.D., Metal Alkoxides, Academic Press, Inc., New York, N.Y. (1978) andalso Teyssie, Ph., Bioul, J. P., Hocks, L. and Ouhadi, T., Chemtech(1977), pp. 192-194.

If the catalyst is to be used to produce a surfactant or otheralkoxylation product using a different starter, an exchange can beperformed as described above. For example, in producing a surfactant,the catalyst of formula (i) hereinabove can be added to a stirred vesselcontaining a surfactant range alcohol or mixture of such alcohols,typically C₁₂ -C₁₄ alcohols. The concentration of catalyst precursorcomposition or Group IIIB metal-containing bimetallic or polymetalliccatalyst composition used can vary over a very broad range, but ideallywould be approximately that desired for the subsequent alkoxylationreaction. The temperature during the exchange reaction may be anytemperature at which the reaction will occur, but, preferably, will bein the range of about 100°-250° C., and pressure may be adjusted toachieve these temperatures. If the exchange procedure is followed, theactivator chosen should have a boiling point of less than about 200° C.to permit it to be readily stripped from the detergent alcohol, most ofwhich boil in the 250° C. range or higher. The resultingalcohol-exchanged product is suitable for use directly as a catalyst inalkoxylation reactions to produce surfactants started with the exchangedalcohol or alcohols.

The catalyst produced by the above-described process is often in theform of a stable slurry of finely divided (e.g., about 5 microns)particles, and containing excess Group IIIB metal-containing compound.

The catalyst precursor composition of formula (ii) hereinabove,including the alcohol-exchanged product thereof, is modified with adivalent or polyvalent oxyacid or a divalent or polyvalent metal salt ofan oxyacid prior to use as catalyst for alkoxylation to provide a narrowdistribution of alkoxylate products. Mixtures of divalent or polyvalentoxyacids and/or mixtures of divalent or polyvalent metal salts ofoxyacids, or cross combination mixtures thereof, can be used in theprocesses of this invention. The modifier can be added at any timeduring the catalyst preparation but generally is added prior to theaddition of a detergent-range alcohol and may be added as a solid ordissolved in an appropriate solvent. While the precise chemical natureof this procedure is not fully understood, the modification does resultin a demonstrable improvement to the overall process in that themolecular weight distribution is narrowed. In addition, modifiedcatalysts tend to require little or no induction period in thealkoxylation reaction, and also increase the reaction rate over that oftheir unmodified counterparts. In contrast, addition of a divalent orpolyvalent oxyacid or a divalent or polyvalent metal salt of an oxyacidto conventional catalysts, such as potassium hydroxide, slows thealkoxylation rate while producing no beneficial effect on the productdistribution.

Alternatively, the modified Group IIIB metal-containing bimetallic orpolymetallic catalysts may be prepared by contacting a Group IIIBmetal-containing compound with an activator under conditions at whichthe Group IIIB metal-containing compound and the activator will react orinteract to form one or more catalytically active derivatives, which arethen reacted with a divalent or polyvalent metal salt of an oxyacidother than a Group IIA metal salt of an oxyacid under conditionseffective to form one or more modified alkoxylation catalysts. Seecopending U.S. patent application Ser. No. 251,434, filed on an evendate herewith, and incorporated herein by reference.

Advantageous results can be obtained if the catalyst is used in its"crude" form, i.e., without separation from its reaction mixture orpurification. Nevertheless, if desired, the catalyst, whether modifiedor not, can be separated from its reaction mixture, purified, dried andstored. Such may be accomplished in a straightforward manner, as bystripping off the excess activator or other organic material containingactive hydrogen, filtering the resulting slurry, reslurrying the wetsolids with a solvent (e.g., tetrahydrofuran) and refiltering, anddrying, preferably under vacuum. The solids thus obtained will becatalytically active, but, frequently, they are substantially lessactive than the catalyst in its "crude" form. Reaction ratenotwithstanding, however, the desired narrow molecular weightdistribution and other benefits can still be obtained.

It is a highly desirable, and quite unexpected, benefit of this aspectof the invention that the overall process embodied in the variousprocedures described above for making catalysts from Group IIIB metalsis remarkably "forgiving" of process variations. Thus, considerableflexibility exists as to the point modifier is added and, withinreasonable limits, how much modifier is used. Similarly, the unreactedactivator may be removed wholly or partially prior to, e.g., an exchangereaction, if used, or it may be left present during the exchangereaction. Moreover, the catalyst may be re-used indefinitely, used andstored in its "crude" form, or purified and dried, with any loss inreaction rate made up by increasing temperature.

The procedures involved in carrying out the process of this inventionare illustrated by the following description directed toward themanufacture of nonionic surfactants.

The manner in which the process of this invention is practiced can beillustrated by the following generalized procedure for preparing aslurry of Group IIIB metal-containing bimetallic or polymetallicalkoxylation catalyst intended for use in the manufacture of "peaked"(narrow molecular weight distribution) linear alcohol ethoxylates(nonionic surfactants).

As applied to the specific case of the production of nonionicsurfactants, the process of this invention is characterized by aconsiderable degree of operational latitude. This is particularly truein the preferred version of the process wherein the modified form of thecatalyst is produced. From the standpoint of the chemistry which takesplace, there are five distinct steps in the preferred preparation of themodified Group IIIB metal-containing bimetallic and polymetalliccatalysts. Steps 1, 2, 3 and 4 involve the following reactions:

Step 1--Reaction of a Group IIIB metal or a Group IIIB metal-containingcompound with a suitable activator to produce a Group IIIBmetal-containing composition.

Step 2--Reaction of a divalent or polyvalent metal other than a GroupIIA metal or other suitable source of divalent or polyvalent metal otherthan a Group IIA metal source with an organic compound containing atleast one active hydrogen to produce a divalent or polyvalentmetal-containing composition.

Step 3--Reaction of the Group IIIB metal-containing composition with thedivalent or polyvalent metal-containing composition to produce acatalyst precursor composition.

Step 4--Reaction of the catalyst precursor composition with a detergentrange alcohol to effect exchange of the activator-derived organicradicals for detergent-range alcohol-derived organic radicals.

During or following the exchange reactions of step 4 the activator,which preferably is substantially more volatile than the detergent-rangealcohol, is removed from the system by distillation. At the conclusionof this operation, the unmodified version of the catalyst is obtained inthe form of an activator-free slurry in the detergent-range alcohol.

In the preparation of the intermediate unmodified form of the Group IIIBmetal-containing bimetallic or polymetallic catalyst, steps 1 and 2 maybe combined into one operation. The Group IIIB metal-containingcomposition prepared in step 1 and the divalent or polyvalentmetal-containing composition prepared in step 2 may be the samecomposition, thereby omitting step 2. Additionally, steps 1 and 4,above, may be combined into one operation wherein the Group IIIB metalor Group IIIB metal-containing compound is reacted with a mixture ofactivator and detergent-range alcohol. Alternatively, step 2 may beomitted and a divalent or polyvalent metal salt of an oxyacid used instep 5 below which is other than a Group IIA metal salt of an oxyacid.In cases where especially effective activators are being used (e.g.,ethylene glycol, 1,2-propylene glycol, ethylene glycol monoethylether,etc.), this alternative procedure of combining the activator with thedetergent-range alcohol is frequently preferred because it tends tominimize color build-up in the catalyst slurry. From the standpoint ofthe final product characteristics, both procedures are equallyacceptable. Modified processes wherein the activator is fed into aslurry of the detergent-range alcohol and the Group IIIB metal base orthe detergent-range alcohol is fed into a slurry (or, in some cases, asolution) of the Group IIIB metal base in the activator are alsooperationally viable, although their use offers no perceived advantageover the batch-charging version.

The preparation of the modified catalyst involves a fifth majorprocessing operation which, like that of steps 1 through 4, is adistinct step in terms of the chemistry which takes place.

Step 5--Treatment of the slurry of unmodified catalyst indetergent-range alcohol with a deficiency of some appropriate modifiersuch as a divalent or polyvalent oxyacid or a divalent or polyvalentmetal salt of an oxyacid or mixtures thereof.

This step provides a highly-active, modified Group IIIB metal-containingbimetallic or polymetallic catalyst in the form of a slurry in thedetergent-range alcohol. The product slurry is normally subjected to anin vacuo drying operation before it is employed in an ethoxylationreaction to manufacture a nonionic surfactant. The modifier charge canbe based either upon the initial Group IIIB metal-containing compoundcharge or, more desirably where possible, upon an "active catalyst"value which is obtained by titrating a sample of the Group IIIBmetal-containing compound/activator reaction mixture for alkalinitycontent using 0.01N alcoholic HCl in the presence of bromothymol blueindicator. When a divalent or polyvalent oxyacid is employed, it isconvenient to use the above procedure. An optional procedure is tofollow the course of the Group IIIB metal-containing compound/activatorreaction by titration and to base the modifier charge upon thealkalinity value obtained when a constant level of alkalinity has beenreached. For example, the modifier is added at a level of about 50% ofthis "constant" alkalinity value. Monitoring of the Group IIIBmetal-containing compound/activator reaction by titration and ultimatelydetermining the modifier charge based upon this analysis, althoughfrequently a preferred procedure, cannot be used with amino-functionalactivators because the amine functionality interferes with thealkalinity analysis. In such instances, the preferred procedure is tobase the modifier charge on the alkalinity value obtained by titratingthe activator-free (stripped) slurry of catalyst in detergent alcohol.

Because of the fact that this process offers such wide operationallatitude, there is no single procedure which can be said to representthe general procedure. This consideration notwithstanding, one procedurewhich will suffice to illustrate the process is as follows:

A Group IIIB metal-containing compound (as commercially supplied) and2-ethoxyethanol (available from Union Carbide Corporation, Danbury,Conn.) are charged to a suitably-sized, agitated vessel equipped with areflux condenser, thermocouple, 10-tray distillation column, and inertgas purge inlet. The reactants are charged in weight ratios ranging from60 to 80 parts of 2-ethoxyethanol to one part of Group IIIBmetal-containing compound. The charge is heated under a nitrogen purgefor a period of 2 to 6 hours at the reflux temperature (about 135° C.)while refluxing solvent is removed overhead continuously orintermittently at a make rate sufficiently slow such that during theentire reaction period only about 10 to 15% of the original solventcharge is removed overhead. The purpose of this operation is to removefrom the system water which was either introduced with the reactants orproduced by chemical reaction. During the reflux period, the reactionmixture is sampled at periodic intervals to monitor the buildup of"alkalinity" which is indicative of the formation of catalyticallyactive materials. The analytical method used for this purpose is atitration with 0.01N HCl in 2-ethoxyethanol using bromothymol blueindicator. When similar "alkalinity" levels are obtained from twosuccessive titrations, the Group IIIB metal-containingcompound/activator reaction step is considered to be finished. The usualtimed period to reach this point is about 4 hours.

The resulting Group IIIB metal-containing composition is then reactedwith a divalent or polyvalent metal-containing composition other than aGroup IIA metal-containing composition to produce a catalyst precursorcomposition. For example, a mixture of aluminum isopropoxide inisopropanol is added to the Group IIIB metal-containing composition andheated at reflux (ca. 80° C.) for a period of about 2 to 6 hours undernitrogen while concurrently removing isopropanol overhead. After aconstant head temperature is maintained, corresponding to2-ethoxyethanol (ca. 135° C.), the heat is removed and the reactionmixture allowed to cool to ambient temperature.

At this point the reaction mixture is diluted with the detergent rangealcohol to be ethoxylated; typically the quantity of alcohol added isabout 100 grams/gram of Group IIIB metal-containing compound (calculatedas Group IIIB metal-containing compound) used in the initial reaction.The resulting mixture is cooled to about 75° C. and treated, underagitation, with sufficient modifier, preferably phosphoric acid or ametal phosphate, to modify about 50% (on an equivalents basis) of thecatalyst precursor reaction mixture.

The temperature is then increased to permit removal of the activatorfrom the reaction mixture by distillation. Distillation is continueduntil the kettle temperature reaches about 215° to 225° C. and both thekettle product and the distillate are free of activator as indicated bygas chromatographic (GC) analysis (e.g., less than 1000 ppm by weightand often less than 100 ppm by weight).

The thus-obtained activator-free slurry of catalyst in detergent alcoholcan either be used directly as a charge to the ethoxylation reactor or,optionally, diluted with sufficient, dry detergent-range alcohol toafford any desired catalyst concentration in the slurry. A final"alkalinity" value on this slurry may, if desired, be obtained by thesame titration procedure described hereinabove.

The above procedure represents but one of many equally viable versionsof this process. Other versions are possible through combinations of theoptions available in the various process steps.

The catalytic alkoxylation reactions of this invention can be effected,for example, by conventional methods such as (1) batch processes; (2)continuous fixed-bed processes; and (3) continuous fluidized reactorprocesses. In a batch reactor, the catalyst is kept suspended in thereactant by shaking or stirring. In a fluidized reactor, the catalyst isat a particular original level. As the velocity of the reactant streamis increased, the catalyst bed expands upward to a second level, and ata critical velocity it enters into violent turbulence. The fluidizedreactor is particularly useful for removing or supplying the heatnecessary to maintain a fixed catalyst temperature. The fluidizedreactor can usually be employed only on a rather large scale since goodfluidization requires a reactor larger than about 1.5 inches indiameter.

The processes of this invention broadly involve the use of Group IIIBmetal-containing bimetallic or polymetallic catalysts for thealkoxylation of active-hydrogen compounds, preferablyhydroxyl-containing compounds, such as, primary or secondary alcohols,diols or triols. Mixtures of active-hydrogen compounds can be used.

Alkoxylation product mixtures prepared by the processes of thisinvention comprise alkoxylation species that can be represented by theformula

    R.sub.10 [(CHR.sub.11 --CHR.sub.12 O).sub.r H].sub.s

wherein R₁₀ is an organic residue of an organic compound having at leastone active hydrogen, s is an integer of at least 1 up to the number ofactive hydrogens contained by the organic compound, R₁₁ and R₁₂ may bethe same or different and can be hydrogen and alkyl (including hydroxy-and halo-substituted alkyl) of, for example, 1 to 28 carbons, and r isan integer of at least 1, say, 1 to about 50.

Organic compounds having active hydrogens include alcohols (mono-, di-and polyhydric alcohols), phenols, carboxylic acids (mono-, di- andpolyacids), and amines (primary and secondary). Frequently, the organiccompounds contain 1 carbon to about 100 or 150 carbons (in the case ofpolyol polymers) and can contain aliphatic and/or aromatic structures.Most often, the organic compounds are selected from the group of mono-,di- and trihydric alcohols having 1 to about 30 carbon atoms. Theorganic compounds having active hydrogens can be the product ofhydroformylation/hydrogenation reactions.

Particularly preferred alcohols are primary and secondary monohydricalcohols which are straight or branched chain such as methanol, ethanol,propanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol,undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol,hexadecanol, octadecanol, isopropyl alcohol, 2-ethylhexanol,sec-butanol, isobutanol, 2-pentanol, 3-pentanol and isodecanol.Particularly suitable alcohols are linear and branched primary alcohols(including mixtures) such as produced by the "Oxo" reaction of C₃ to C₂₀olefins. The alcohols may also be cycloaliphatic such as cyclopentanol,cyclohexanol, cycloheptanol, cyclooctanol, as well as aromaticsubstituted aliphatic alcohols such as benzyl alcohol, phenylethylalcohol, and phenylpropyl alcohol. Other aliphatic structures include2-methoxyethanol and the like.

Phenols include alkylphenyls of up to 30 carbons such as p-methylphenol,p-ethylphenol, p-butylphenol, p-heptylphenol, p-nonylphenol,dinonylphenol and p-decylphenol. The aromatic radicals may contain othersubstituents such as halide atoms.

Alcohols (polyols) having 2 or more hydroxyl groups, e.g., about two tosix hydroxyl groups and have 2 to 30 carbons, include glycols such asethylene glycol, propylene glycol, butylene glycol, pentylene glycol,hexylene glycol, neopentylene glycol, decylene glycol, diethyleneglycol, triethylene glycol and dipropylene glycol. Other polyols includeglycerine, 1,3-propanediol, pentaerythritol, galactitol, sorbitol,mannitol, erythritol, trimethylolethane and trimethylolpropane.

The alkylene oxides which provide the oxyalkylene units in theethoxylated products include alkylene oxides such as ethylene oxide,propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2- and2,3-pentylene oxide, cyclohexylene oxide, 1,2-hexylene oxide,1,2-octylene oxide, and 1,2-decylene oxide; epoxidized fatty alcoholssuch as epoxidized soybean fatty alcohols and epoxidized linseed fattyalcohols; aromatic epoxides such as styrene oxide and 2-methylstyreneoxide; and hydroxy- and halogen-substituted alkylene oxides such asglycidol, epichlorhydrin and epibromhydrin. The preferred alkyleneoxides are ethylene oxide and propylene oxide.

The selection of the organic residue and the oxyalkylene moieties isbased on the particular application of the resulting alkoxylationproduct. Advantageously, narrow distributions can be obtained using awide variety of compounds having active hydrogens, especially monohydricalcohols, which provide desirable surfactants. Because of the narrowdistribution of the alkoxylation product mixture, especially attractivealkoxylation products are surfactants in which certain hydrophilic andlipophilic balances are sought. Hence, the organic compound oftencomprises a monohydric alcohol of about 8 to 20 carbons and the alkyleneoxide comprises ethylene oxide.

While the processes described herein are capable of selectivelyproviding narrow distributions of alkoxylates with the most prevalenthaving as low as one mole of oxyalkylene per mole of active hydrogensite, a particular advantage exists in the ability to provide a narrowdistribution at higher levels of alkoxylation, e.g., wherein the mostprevalent specie has at least 4 oxyalkylene units. For some surfactantapplications, the most prevalent alkoxylation specie has 6, 7, 8, 9, 10,11 or 12 oxyalkylene units per active hydrogen site. For many surfactantapplications, it has been found that a relatively few species providethe desired activity, i.e., a range of plus or minus two oxyalkyleneunits. Hence, the compositions of this invention are particularlyattractive in that the range of alkoxylation is narrow, but not sonarrow that a range of activity is lost.

Moreover, the relatively symmetrical distribution of alkoxylate speciesthat can be provided by this invention enhances that balance whileproviding a mixture that exhibits desirable physical properties such ascloud point, freeze point, viscosity, pour point and the like. For manyalkoxylation mixtures of this invention, the species falling within therange of n plus or minus two comprise at least about 75, say, about 80to 95, sometimes 85 to 95, weight percent of the composition.Importantly, the compositions can be provided such that no singlealkoxylation product is in an amount of greater than 50 weight percentof the composition, and, most often, the most prevalent specie is in anamount of 20 to about 30 weight percent, e.g., about 22 to 28, weightpercent, to enhance the balance of the composition.

Another class of alkoxylation product mixtures are thepoly(oxyethylene)glycols. For instance, triethylene glycol andtetraethylene glycol find application in gas dehydration, solventextraction and in the manufacture of other chemicals and compositions.These glycols can be prepared by the ethoxylation of ethylene glycol anddiethylene glycol. Advantageous processes of this invention enableethoxylate product compositions containing at least about 80, say, about80 to 95, weight percent of triethylene glycol and tetraethylene glycol.

Among the most commercially important alkoxylation products are thosewhich utilize water or an alcohol (monols, glycols, polyols, etc.) asstarter (initiator) and ethylene oxide, propylene oxide, or an ethyleneoxide/propylene oxide mixture as the 1,2-alkylene oxide monomer. Suchalcohol ethoxylates encompass a myriad of structures, compositions andmolecular weights intended for service in a diversity of applicationsranging from heavy duty industrial end uses such as solvents andfunctional fluids to ultra-sophisticated, consumer-oriented end usessuch as in pharmaceutical, personal care and household goods. The GroupIIIB metal-containing bimetallic or polymetallic catalysts of theinstant invention find utility in the manufacture of a broad range ofalkoxylation products, but are particularly useful in the manufacture ofalkoxylates designed for service in sophisticated, consumer-oriented enduse areas of application where product quality demands are stringent.Among the many types of alkoxylates which are used in such applications,two of the most prominent are the poly(oxyethylene)glycols and the fattyalcohol ethoxylates. The poly(oxyethylene)glycols, known under suchtradenames as CARBOWAX®, POLYGLYCOL E®, PLURACOL E®, etc., aremanufactured by ethoxylation of ethylene glycol or one of itshomologues; they are produced over a molecular weight range of about 200to about 8,000. The fatty alcohol ethoxylates, known under suchnon-ionic surfactant tradenames as NEODOL®, ALFONIC®, TERGITOL®, etc.,are manufactured by ethoxylation of linear or branched C₁₀ -C₁₆saturated alcohols; they are produced over a molecular weight range ofabout 300 to about 800. It is in the production of these and otherperformance type, premium quality ethoxylates that the Group IIIBmetal-containing bimetallic or polymetallic catalysts of the instantinvention offer maximum advantages relative to the usual homogeneousethoxylation catalysts (NaOH, KOH, etc.).

This invention can be illustrated by the following examples.

EXAMPLE 1

Into a 1-liter reaction flask equipped with a reflux condenser,thermocouple, mechanical stirrer and a gas purge inlet was added 310grams of ethylene glycol and 14.5 grams of lanthanum oxide. Theresulting mixture was heated under vacuum (180 millimeters) at reflux(ca. 148° C.) for a period of 4 hours during which time 135 grams ofdistillate was removed overhead and analyzed for water. The reactionmixture was then cooled in an ice bath to a temperature of 5° C. and2.14 grams (0.018 moles) of phosphoric acid were added to the flask. Themixture was stirred for a period of 10 minutes and 510 grams of Alfol®1214, a mixture of C₁₂₋₁₄ linear, fatty alcohols (approximately 55/45weight ratio) commercially available from Vista Chemical Company,Houston, Tex., were added to the reaction flask. The reaction mixturewas then heated under vacuum (3-4 millimeters) and ethylene glycolremoved overhead. When the kettle temperature reached 132° C., the heatwas removed and the contents allowed to cool to ambient temperatureunder a nitrogen blanket until use. A quantity of this catalyst was usedto make a batch preparation of a nonionic surfactant as described inExample 4 hereinafter.

EXAMPLE 2

Into a 1-liter reaction flask equipped with a reflux condenser,thermocouple, mechanical stirrer and a gas purge inlet was added 306grams of ethylene glycol and 30.6 grams of cerium acetate. The resultingmixture was heated under vacuum (16 millimeters) at reflux (ca. 106° C.)for a period of 4.5 hours during which time 105 grams of distillate wasremoved overhead. The reaction mixture was then cooled in an ice bath toa temperature of 5° C. and 3.0 grams (0.026 moles) of phosphoric acidwere added to the flask. The mixture was stirred for a period of 10minutes and 510 grams of Alfol® 1214, a mixture of C₁₂₋₁₄ linear, fattyalcohols (approximately 55/45 weight ratio) commercially available fromVista Chemical Company, Houston, Tex., were added to the reaction flask.The reaction mixture was then heated under vacuum (3-4 millimeters) andethylene glycol removed overhead. When the kettle temperature reached129° C., the heat was removed and the contents allowed to cool toambient temperature under a nitrogen blanket until use. A quantity ofthis catalyst was used to make a batch preparation of a nonionicsurfactant as described in Example 5 hereinafter.

EXAMPLE 3

Into a 1-liter reaction flask equipped with a reflux condenser,thermocouple, mechanical stirrer and a gas purge inlet was added 308grams of ethylene glycol, 14.50 grams (0.0445 moles) of lanthanum oxideand 4.88 grams (0.0222 moles) of zinc acetate dihydrate. The resultingmixture was heated under vacuum (150 millimeters) at reflux (ca. 150°C.) for a period of 4 hours during which time 158 grams of distillatewas removed overhead and analyzed for water. The reaction mixture wasthen cooled in an ice bath to a temperature of 5° C. and 3.0 grams(0.026 moles) of phosphoric acid were added to the flask. The mixturewas stirred for a period of 20 minutes and 516 grams of Alfol® 1214, amixture of C₁₂₋₁₄ linear, fatty alcohols (approximately 55/45 weightratio) commercially available from Vista Chemical Company, Houston,Tex., were added to the reaction flask. The reaction mixture was thenheated under vacuum (3-4 millimeters) and ethylene glycol removedoverhead. When the kettle temperature reached 131° C., the heat wasremoved and the contents allowed to cool to ambient temperature under anitrogen blanket until use. A quantity of this catalyst was used to makea batch preparation of a nonionic surfactant as described in Example 6hereinafter.

EXAMPLES 4 THROUGH 6

The general procedure described hereinabove was used to produce nonionicsurfactants. The reactor for these preparations was a 2 gallon stirredautoclave equipped with an automatic ethylene oxide feed system whereina motor valve controlled the feed of ethylene oxide to maintain about 60psig pressure. Into the 2 gallon stirred autoclave was added Alfol®1214, ethylene oxide and a catalyst slurry (moles of starting metalexclusive of any metal in added modifier) specified in Table A below inthe amounts specified in Table A. The reactions were conducted under anitrogen atmosphere (20 psig) at a temperature of 140° C. The ethyleneoxide feed time and maximum reaction rate are also specified in Table A.The molecular weight distribution of the nonionic surfactant productswas determined by gas chromatographic analysis (area %) and the resultsare given in Table A.

                  TABLE A                                                         ______________________________________                                        Preparation of Nonionic Surfactants                                           Example            4        5       6                                         ______________________________________                                        Ethoxylation Process                                                          Alfol ® 1214 (grams)                                                                         500      506     500                                       Ethylene oxide (grams)                                                                           766      771     764                                       Catalyst prepared in Example No.                                                                 1        2       3                                         Catalyst (moles of metal(s))                                                                     0.044    0.089   0.067                                     Ethylene oxide feed                                                                              26       46      66                                        time (minutes)                                                                Maximum reaction   36       41      14.4                                      rate (grams/minute)                                                           Product Molecular Weight                                                      Distribution                                                                  E.sub.0            3.70     1.81    1.25                                      E.sub.1            1.76     1.52    1.25                                      E.sub.2            2.36     2.78    2.87                                      E.sub.3            5.10     6.56    7.33                                      E.sub.4            10.42    12.89   14.32                                     E.sub.5            17.05    18.74   21.17                                     E.sub.6            20.08    20.22   22.04                                     E.sub.7            17.03    16.30   15.46                                     E.sub.8            10.97    10.33   9.29                                      E.sub.9            5.90     5.41    4.75                                      E.sub.10           3.06     2.38    --                                        E.sub.11           1.62     0.73    --                                        E.sub.12           0.66     --      --                                        ______________________________________                                    

The results from Table A demonstrate the effectiveness oflanthanum-containing and cerium-containing bimetallic or polymetalliccatalysts modified with phosphoric acid. As illustrated by Examples 4through 6, nonionic surfactants were prepared having a narrowdistribution of alkoxylation species with at least one alkoxylationspecie constituting at least about 20 weight percent of the productmixture.

Although the invention may have been illustrated by the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

I claim:
 1. A method for providing an alkoxylation catalystcomprising:(a) reacting or solubilizing, at least partially, a GroupIIIB metal or a Group IIIB metal-containing compound by mixing with anactivator having the formula

    Z.sub.a --X--Q--Y--Z'.sub.b

wherein X and Y are the same or different electronegative, heteroatomsselected from the group consisting of oxygen, nitrogen, sulfur andphosphorus; a and b are the same or different integers satisfying thevalency requirements of X and Y; Q is an organic radical which iselectropositive or essentially neutral relative as to X and/or Y; Z andZ' are the same or different and are either hydrogen or an organicradical which does not prevent said reacting or solubilizing, therebyforming a Group IIIB metal-containing composition which has titratablealkalinity; (b) reacting a divalent or polyvalent metal other than aGroup IIA metal or a divalent or polyvalent metal-containing compoundother than a Group IIA metal-containing compound with an organiccompound having at least one active hydrogen to produce a divalent orpolyvalent metal-containing composition; (c) reacting the Group IIIBmetal-containing composition with the divalent or polyvalentmetal-containing composition under effective reaction conditions toproduce a catalyst precursor composition; and (d) reacting the catalystprecursor composition with a divalent or polyvalent oxyacid or adivalent or polyvalent metal salt of an oxyacid or mixtures thereofunder effective reaction conditions to produce the alkoxylationcatalyst.
 2. The method of claim 1 wherein steps (a) and (b) arecombined into one step.
 3. The method of claim 1 wherein the Group IIIBmetal-containing compound is selected from oxides, hydroxides,carboxylates, alcoholates, ammoniates, amides, nitrides, thiocyanates,thiolates, carbides, thiophenoxides and substances to which saidcompounds are converted in situ in said method.
 4. The method of claim 3wherein the Group IIIB metal-containing compound is a carboxylateselected from acetates, formates, oxalates, citrates, benzoates,laurates, stearates and substances to which said compounds are convertedin situ in said method.
 5. The method of claim 1 wherein the Group IIIBmetal-containing compound is a lanthanum-containing compound.
 6. Themethod of claim 1 wherein the Group IIIB metal-containing composition isa lanthanum-containing alcoholate or a cerium-containing carboxylate. 7.The method of claim 1 wherein the activator has the formula: ##STR7##wherein R₆, R₇, R₈ and R₉ are the same or different and are selectedfrom the group consisting of hydrogen and lower alkyl or alkylene groupsof one to four carbon atoms.
 8. The method of claim 1 wherein theactivator is ethylene glycol.
 9. The method of claim 1 wherein theactivator is 2-ethoxyethanol.
 10. The method of claim 1 wherein thedivalent or polyvalent metal salt of an oxyacid is a metal phosphate.11. The method of claim 1 wherein the divalent or polyvalent metal saltof an oxyacid is a mixture of a metal sulfate and a metal phosphate. 12.The method of claim 1 wherein the divalent or polyvalent oxyacid isphosphoric acid.
 13. The method of claim 1 wherein the divalent orpolyvalent oxyacid is a mixture of sulfuric acid and phosphoric acid.14. The method of claim 1 wherein the divalent or polyvalentmetal-containing compound is selected from oxides, hydroxides,carboxylates, alcoholates, ammoniates, amides, nitrides, thiocyanates,thiolates, carbides, thiophenoxides and substances to which saidcompounds are converted in situ in said method.
 15. The method of claim14 wherein the divalent or polyvalent metal-containing compound is acarboxylate selected from acetates, formates, oxalates, citrates,benzoates, laurates, stearates and substances to which said compoundsare converted in situ in said method.
 16. The method of claim 1 whereinthe divalent metal-containing composition is a metal-containingalcoholate.
 17. The method of claim 1 wherein the divalent or polyvalentmetal-containing composition contains a metal selected from aluminum,zinc, thorium, zirconium, lanthanum, cerium and titanium.
 18. The methodof claim 1 comprising the additional step of reacting the alkoxylationcatalyst with an alcohol under conditions at which an alcohol exchangereaction occurs with the alkoxylation catalyst, thereby producing acorresponding alcohol derivative.
 19. The method of claim 18 wherein thealcohol is n-dodecanol.
 20. The method of claim 18 wherein the alcoholis a mixture of C₁₂ -C₁₄ alcohols.
 21. The method of claim 18 whereinthe alcohol is a product of a hydroformylation/hydrogenation reaction.22. The method of claim 1 comprising the additional step of removingsome or all activator which is not bound to the Group IIIB metal or thedivalent or polyvalent metal.
 23. The method of claim 1 wherein about 25to about 90% of the normal equivalence of the divalent or polyvalentoxyacid or the divalent or polyvalent metal salt of an oxyacid to theGroup IIIB metal and the divalent or polyvalent metal is added duringstep (d).
 24. An alkoxylation catalyst prepared by the method ofclaim
 1. 25. An alkoxylation catalyst prepared by the method of claim18.
 26. An alkoxylation catalyst having the formula:

    (R.sub.1 --X.sub.1 --M.sub.1).sub.f --Y.sub.1 --(M.sub.3 --Y.sub.2).sub.j --(M.sub.2 --X.sub.2 --R.sub.2).sub.g

wherein: R₁ and R₂ are independently hydrogen or an organic residue ofan organic compound having at least one active hydrogen; X₁ and X₂ areindependently oxygen, sulfur or nitrogen; M₁, M₂ and M₃ areindependently a divalent or polyvalent metal other than a Group IIAmetal provided at least one of M₁, M₂ and M₃ is a Group IIIB metal; Y₁and Y₂ are independently a divalent or polyvalent oxyacid anion ofvalence 2 to 6, oxygen, sulfur or nitrogen provided at least one of Y₁and Y₂ is a divalent or polyvalent oxyacid anion of valence 2 to 6; j isan integer having a value of from 0 to about 100; and f and g areintegers having a value such that the sum f+g is equal to the valence ofY₁ when j has a value of 0, and f and g are integers having a value suchthat the sum f+g is equal to the valence of Y₁ plus (M₃ -Y₂)_(j) when jhas a value other than 0.